On the Alloying and Properties of Tetragonal Nb₅Si₃ in Nb-Silicide Based Alloys

The alloying of Nb₅Si₃ modifies its properties. Actual compositions of (Nb,TM)₅X₃ silicides in developmental alloys, where X = Al + B + Ge + Si + Sn and TM is a transition and/or refractory metal, were used to calculate the composition weighted differences in electronegativity (Δχ) and an average valence electron concentration (VEC) and the solubility range of X to study the alloying and properties of the silicide. The calculations gave 4.11 < VEC < 4.45, 0.103 < Δχ < 0.415 and 33.6 < X < 41.6 at.%. In the silicide in Nb-24Ti-18Si-5Al-5Cr alloys with single addition of 5 at.% B, Ge, Hf, Mo, Sn and Ta, the solubility range of X decreased compared with the unalloyed Nb₅Si₃ or exceeded 40.5 at.% when B was with Hf or Mo or Sn and the Δχ decreased with increasing X. The Ge concentration increased with increasing Ti and the Hf concentration increased and decreased with increasing Ti or Nb respectively. The B and Sn concentrations respectively decreased and increased with increasing Ti and also depended on other additions in the silicide. The concentration of Sn was related to VEC and the concentrations of B and Ge were related to Δχ. The alloying of Nb₅Si₃ was demonstrated in Δχ versus VEC maps. Effects of alloying on the coefficient of thermal expansion (CTE) anisotropy, Young's modulus, hardness and creep data were discussed. Compared with the hardness of binary Nb₅Si₃ (1360 HV), the hardness increased in silicides with Ge and dropped below 1360 HV when Al, B and Sn were present without Ge. The Al effect on hardness depended on other elements substituting Si. Sn reduced the hardness. Ti or Hf reduced the hardness more than Cr in Nb₅Si₃ without Ge. The (Nb,Hf)₅(Si,Al)₃ had the lowest hardness. VEC differentiated the effects of additions on the hardness of Nb₅Si₃ alloyed with Ge. Deterioration of the creep of alloyed Nb₅Si₃ was accompanied by decrease of VEC and increase or decrease of Δχ depending on alloying addition(s)

On the microstructure and properties of Nb-12Ti-18Si-6Ta-5Al-5Cr-2.5W-1Hf (at.%) silicide-based alloys with Ge and Sn additions

The microstructures and properties of the alloys JZ3 (Nb-12.4Ti-17.7Si-6Ta-2.7W-3.7Sn-4.8Ge-1Hf-4.7Al-5.2Cr) and JZ3+(Nb-12.4Ti-19.7Si-5.7Ta-2.3W-5.7Sn-4.9Ge-0.8Hf-4.6Al-5.2Cr) were studied. The densities of both alloys were lower than the densities of Ni-based superalloys and many of the refractory metal complex concentrated alloys (RCCAs) studied to date. Both alloys had Si macrosegregation and the same phases in their as cast and heat treated microstructures, namely βNb5Si3, αNb5Si3, A15-Nb3X (X = Al, Ge, Si, Sn), C14-Cr2Nb and solid solution. W-rich solid solutions were stable in both alloys. At 800 °C only the alloy JZ3 did not show pest oxidation, and at 1200 °C a thin and well adhering scale formed only on JZ3+. The alloy JZ3+ followed parabolic oxidation with rate constant one order of magnitude higher than the single crystal Ni-superalloy CMSX-4 for the first 14 h of oxidation. The oxidation of both alloys was superior to that of RCCAs. Both alloys were predicted to have better creep at the creep goal condition compared with the superalloy CMSX-4. Calculated Si macrosegregation, solid solution volume fractions, chemical compositions of solid solution and Nb5Si3, weight changes in isothermal oxidation at 800 and 1200 °C using the alloy design methodology NICE agreed well with the experimental results

Phase equilibria in the Nb-rich region of Al-Nb-Sn at 900 and 1200 °C

The Al-Nb-Sn phase diagram was studied experimentally in the Nb-rich region to provide important phase equilibria information for alloy design of Nb-silicide based materials for aero engine applications. Three alloys were produced: Nb-17Al-17Sn, Nb-33Al-13Sn and Nb-16Al-20Sn (at.%). As-cast and heat-treated alloys (900 and 1200 °C) were analysed using XRD (X-ray diffraction) and SEM/EDS (scanning electron microscopy/ electron dispersive x-ray spectroscopy). Tin showed a high solubility in Nb2Al, reaching up to 21 at.% in the Sn-rich areas, substituting for Al atoms. Tin and Al also substituted for each other in the A15 phases (Nb3Al and Nb3Sn). Tin showed limited solubility in NbAl3, not exceeding 3.6 at.% as it substituted Al atoms. The solubility of Al in NbSn2 varied from 4.8 to 6.8 at.%. A ternary phase, Nb5Sn2Al with the tI32 W5Si3 crystal structure, was found to be stable. This phase was observed in the 900 °C heat-treated samples, but not in the 1200 °C heated samples

Characterization of LiMxFe1–xPO4 (M = Mg, Zr, Ti) Cathode Materials Prepared by the Sol-Gel Method

A series of LiMxFe12xPO4 (M 5 Mg,Zr,Ti) phosphates were synthesized via a sol-gel method. Transmission electron microscopy observations show that LiMxFe12xPO4 particles consist of nanosize crystals, ranging from 40 to 150 nm. High-resolution TEM analysis reveals that a layer of amorphous carbon was coated on the surface of the LiMxFe12xPO4 particles, which substantially increases the electronic conductivity of LiMxFe12xPO4 electrodes. The doped LiMxFe12xPO4 powders are phase pure. Near full capacity ~170 mAh/g! was achieved at the C/8 rate at room temperature for LiMxFe12xPO4 electrodes. The doped LiMxFe12xPO4 electrodes demonstrated better electrochemical performance than that of undoped LiFePO4 at high rate

CMAS Reactive Coatings for TBCs

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Synthesis and Characterization of LiFePO4 and LiTi0.01Fe0.99PO4 Cathode Materials

Nanocrystalline LiFePO4 and doped LiTi0.01Fe0.99PO4 powders were synthesized via a sol-gel preparation route. High-resolution tunneling electron microscopy observation and energy dispersive spectroscopy, mapping show the homogeneous distribution of dopant Ti cations in the crystals. Fe and O K -edge X-ray absorption near-edge structure (XANES) measurements show that Ti4+ doping induces an increased unoccupied d-state in LiFePO4, resulting in an enhanced p-type semiconductivity. In situ Fe K -edge XANES measurements of Ti-doped and undoped LiFePO4 electrodes have been performed to determine the change of Fe valence during the lithium intercalation and de-intercalation processes. Both LiFePO4 and doped LiTi0.01Fe0.99PO4 cathodes demonstrate good electrochemical performance

Synthesis and Characterization of LiFePO4 and LiTi0.01Fe0.99PO4 Cathode Materials

Nanocrystalline LiFePO4 and doped LiTi0.01Fe0.99PO4 powders were synthesized via a sol-gel preparation route. High-resolution tunneling electron microscopy observation and energy dispersive spectroscopy, mapping show the homogeneous distribution of dopant Ti cations in the crystals. Fe and O K -edge X-ray absorption near-edge structure (XANES) measurements show that Ti4+ doping induces an increased unoccupied d-state in LiFePO4, resulting in an enhanced p-type semiconductivity. In situ Fe K -edge XANES measurements of Ti-doped and undoped LiFePO4 electrodes have been performed to determine the change of Fe valence during the lithium intercalation and de-intercalation processes. Both LiFePO4 and doped LiTi0.01Fe0.99PO4 cathodes demonstrate good electrochemical performance

Ab initio study of ternary W5Si3 type TM5Sn2X compounds (TM = Nb, Ti and X = Al, Si)

The adhesion of the scale formed on Nb-silicide based alloys at 1473 K improves when Al and Sn are in synergy with Si and Ti. This improvement is observed when there is segregation of Sn in the microstructure below the alloy/scale interface and a layer rich in intermetallics that include TM5Sn2X compounds is formed at the interface. Data for the ternary compounds is scarce. In this paper elastic and thermodynamic properties of the Nb5Sn2Al, Ti5Sn2Si, Ti5Sn2Al and Nb5Sn2Si compounds were studied using the first-principles, pseudopotential plane-wave method based on density functional theory. The enthalpy of formation of the ternary intermetallics was calculated using the quasi-harmonic approximation. The calculations suggest that the Nb5Sn2Si is the stiffest; that the Nb5Sn2Al and Ti5Sn2Si are the most and less ductile phases respectively; and that Nb significantly increases the bulk, shear and elastic moduli of the ternary compound compared with Ti